JP6750363B2 - Laminates, metal-clad laminates and printed wiring boards - Google Patents

Description

The present invention relates to a laminate, a metal-clad laminate and a printed wiring board. More specifically, the present invention relates to a printed wiring board suitable for a semiconductor package mounted on a network device such as a network server, and a laminate and a metal-clad laminate used for the same.

Along with the increase in speed and capacity of computer networks, semiconductor packages mounted on network devices such as network servers are required to have excellent high-speed signal transmission characteristics. Along with this, printed wiring boards for semiconductor packages are required to have low relative permittivity and low dielectric loss tangent and low transmission loss of high-speed signals.

Further, since these printed wiring boards must be thin and have high density, they are apt to cause a problem of warpage during mounting, have low thermal expansion (coefficient of thermal expansion is close to that of a silicon chip), and have high elasticity. ing.

As a laminate used for a printed wiring board for high-speed signal transmission, a double-sided copper clad laminate having a glass woven cloth coated with a fluororesin layer (see Patent Document 1) is known, while it has low thermal expansion. As a laminate used for a printed wiring board having high elasticity, a resin-impregnated base material in which a resin composition containing polyphenylene oxide, a crosslinkable polymer and a crosslinkable monomer is impregnated in a base material such as glass cloth is used. A known laminated plate (see Patent Document 2) is known.

Japanese Patent No. 5331314 Japanese Examined Patent Publication No. 6-69746

However, the laminate having a fluororesin layer has a problem that it has a low relative permittivity and a low dielectric loss tangent, but is excellent in high-speed signal transmission characteristics, but is poor in workability and adhesion to plating. Further, the laminated plate using polyphenylene oxide as a raw material is excellent in workability, but it cannot be said that the relative permittivity and the dielectric loss tangent are sufficiently low, and there is a problem that it is inferior in the transmission characteristics of high-speed signals. Furthermore, a laminated plate using a glass woven fabric impregnated with these resins generally tends to have a low elastic modulus when trying to lower the thermal expansion coefficient, and there is room for improvement in terms of achieving both low thermal expansion and high elasticity. There is.

The present invention has been made in view of such circumstances, has a low relative permittivity and dielectric loss tangent, has low thermal expansion and high elasticity, and is unlikely to cause a problem of warpage, a metal-clad laminate. An object is to provide a body and a printed wiring board using them.

As a result of intensive studies to solve the above problems, the present inventors have obtained the following findings.

That is, a resin composition containing a specific compound has a feature of low relative dielectric constant and low dielectric loss tangent, and when a wiring pattern is formed on the surface of a resin layer made of such a resin composition, excellent high speed is achieved. The transmission characteristics of the signal can be obtained.

In addition, a laminated body having resin layers on both sides of a glass substrate has a feature of low thermal expansion and high elasticity. A printed wiring board is produced using the laminated body, and an IC chip is mounted to produce a semiconductor package. In this case, it is possible to reduce the warpage that occurs during mounting, as compared with the case of using the conventional glass cloth base resin laminate.

The present invention has been completed based on these findings, and has as its gist the following [1] to [5].
[1] A glass substrate and resin layers provided on both sides of the glass substrate, wherein at least one of the resin layers contains a maleimide group and a compound having a divalent group bonded to the maleimide group. A laminate comprising a resin composition, wherein the divalent group includes a saturated or unsaturated divalent hydrocarbon group bonded to a maleimide group and at least two imide groups other than the maleimide group.
[2] The laminate according to [1], wherein the compound has a weight average molecular weight of 500 to 10,000.
[3] The laminate according to [1] or [2], wherein the resin composition further contains an inorganic filler.
[4] A laminate according to any one of [1] to [3], and a metal foil provided on at least one surface of the resin layer in the laminate opposite to the glass substrate. A metal-clad laminate comprising.
[5] A laminate according to any one of [1] to [3], and a circuit layer provided on at least one surface of the resin layer in the laminate opposite to the glass substrate. Prepare a printed wiring board.

According to the present invention, a laminate, a metal-clad laminate, and a printed wiring board using the same, which have a low relative dielectric constant and a low dielectric loss tangent, have low thermal expansion and high elasticity, and are unlikely to cause warpage problems, are provided. can do.

It is a typical sectional view showing the layered product concerning this embodiment.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[Laminate]
The laminated body of the present embodiment includes a glass substrate and resin layers provided on both surfaces of the glass substrate. FIG. 1 is a schematic cross-sectional view showing a laminated body according to this embodiment. As shown in FIG. 1, the laminated body 10 includes a glass substrate 1 and a resin layer 13 a and a resin layer 13 b provided on both surfaces of the glass substrate 1.

(Glass substrate)
The thickness of the glass substrate according to the present embodiment can be appropriately set according to the application and is not particularly limited, but is preferably 30 to 500 μm, more preferably 30 to 300 μm, and further preferably 50 to 300 μm. preferable. When the thickness of the glass substrate is within the above range, not only can the printed wiring board according to the present embodiment be made thinner, but also ease of handling and reliability can be secured.

The size of the glass substrate is not particularly limited, but from the viewpoint of easy handling, the width is 10 to 1000 mm and the length is 10 to 3000 mm (the length is appropriately applied when used in a roll). preferable. From the same viewpoint, it is more preferable that the width is 25 to 550 mm and the length is 25 to 550 mm.

The material for the glass substrate is not particularly limited. Examples of the material for the glass substrate include glass such as alkali silicate glass, non-alkali glass, and quartz glass. However, borosilicate glass is preferable because it has a thermal expansion coefficient close to that of a silicon chip.

(Resin layer)
The resin layer according to the present embodiment is provided on both surfaces of the glass substrate, and at least one of the resin layers contains a maleimide group and a compound having a divalent group bonded to the maleimide group. Consists of.

The resin layer made of such a resin composition has not only dielectric characteristics comparable to those of the fluororesin layer, but also high adhesiveness, high heat resistance and chemical solution stain resistance equivalent to those of the resin composition containing polyphenylene oxide and the like. ..

(Resin composition)
As described above, the resin composition according to this embodiment contains a compound having a maleimide group and a divalent group bonded to the maleimide group. The divalent group includes at least two imide groups other than a saturated or unsaturated divalent hydrocarbon group bonded to a maleimide group and a maleimide group.

<Compound having maleimide group and divalent group bonded to maleimide group>
A compound having a maleimide group and a divalent group bonded to the maleimide group according to the present embodiment, wherein the divalent group is a saturated or unsaturated divalent hydrocarbon group and a maleimide group bonded to the maleimide group. A compound containing at least two imide groups other than is sometimes referred to as “component (A)”. Further, in the component (A), a maleimide group is a “structure (a)”, a divalent group bonded to a maleimide group is a “structure (b)”, and a saturated or unsaturated divalent carbonized bond is bonded to a maleimide group. The hydrogen group may be referred to as “structure (b1)” and at least two imide groups other than the maleimide group may be referred to as “structure (b2)”. By using the component (A), it is possible to obtain a resin composition having high-frequency characteristics and high adhesiveness with a conductor.

The structure (a) is not particularly limited and is a general maleimide group. The structure (a) is bonded to the structure (b1) in the structure (b) described later, but the bonding position with the structure (b1) in the structure (a) is not limited. Examples of the bonding position of the structure (a) with the structure (b1) include a nitrogen atom of a maleimide group as represented by the following formula (XIV).

The structure (b) includes the structure (b1) and the structure (b2). Of these, the structure (b1) is bonded to the structure (a).

The saturated or unsaturated divalent hydrocarbon group in the structure (b1) is not particularly limited, and may be a saturated or unsaturated divalent linear hydrocarbon group, a saturated or unsaturated divalent branched hydrocarbon group. It may be either a group or a saturated or unsaturated divalent cyclic hydrocarbon group. Further, the unsaturated divalent cyclic hydrocarbon group may be an aromatic group. The saturated or unsaturated divalent hydrocarbon group may have 8 to 300, 8 to 250, 8 to 200 or 8 to 100 carbon atoms. The structure (b1) is preferably an alkylene group having 8 to 300, 8 to 250, 8 to 200 or 8 to 100 carbon atoms, which may have a branch, and has a C 10 to 70 branch. It is more preferable that it is an alkylene group which may be present, and it is still more preferable that it is an alkylene group which has a carbon number of 15 to 50 and may be branched. When the component (A) has the structure (b1), the flexibility of the resin composition according to the present embodiment is improved, and the resin film produced from the resin composition is easy to handle (tackiness, cracking, powder drop). Etc.) and strength can be increased. Further, the structure (b1) having the above carbon number is preferable because the molecular structure can be easily three-dimensionalized and the free volume of the polymer can be increased to lower the density, that is, lower the dielectric constant.

Examples of the structure (b1) include an alkylene group such as a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, an octadecylene group, and a nonadecylene group; an arylene group such as a benzylene group, a phenylene group, and a naphthylene group; Examples thereof include an arylene alkylene group such as a phenylene methylene group, a phenylene ethylene group, a benzyl propylene group, a naphthylene methylene group and a naphthylene ethylene group; and an arylene alkylene group such as a phenylene dimethylene group and a phenylene diethylene group.

From the viewpoint of high-frequency characteristics, low thermal expansion, adhesiveness with a conductor, heat resistance, and low hygroscopicity, a group represented by the following formula (II) is particularly preferable as the structure (b1).

In formula (II), R ² and R ³ each independently represent an alkylene group having 4 to 50 carbon atoms. From the viewpoint of further improving flexibility and easiness of synthesis, R ² and R ³ are each independently preferably an alkylene group having 5 to 25 carbon atoms, and more preferably an alkylene group having 6 to 10 carbon atoms. It is more preferably an alkylene group having 7 to 10 carbon atoms.

In formula (II), R ⁴ represents an alkyl group having ⁴ to 50 carbon atoms. From the viewpoint of further improving flexibility and easiness of synthesis, R ⁴ is preferably an alkyl group having 5 to 25 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms, and having 7 to 7 carbon atoms. More preferably, it is 10 alkyl groups.

In formula (II), R ⁵ represents an alkyl group having 2 to 50 carbon atoms. From the viewpoint of further improving flexibility and easiness of synthesis, R ⁵ is preferably an alkyl group having 3 to 25 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and 5 to 5 carbon atoms. More preferably, it is 8 alkyl groups.

From the viewpoint of fluidity and circuit embeddability, it is preferable that a plurality of structures (b1) are present in the component (A). In that case, the structures (b1) may be the same or different. For example, the component (A) preferably has 2 to 40 structures (b1), more preferably 2 to 20 structures (b1), and has 2 to 10 structures (b1). More preferably.

The structure (b2) is not particularly limited, and examples thereof include groups represented by the following formula (I).

In formula (I), R ¹ represents a tetravalent organic group. R ¹ is not particularly limited as long as it is a tetravalent organic group, but for example, from the viewpoint of handleability, it may be a hydrocarbon group having 1 to 100 carbon atoms or a hydrocarbon group having 2 to 50 carbon atoms. Or a hydrocarbon group having 4 to 30 carbon atoms may be used.

R ¹ may contain a substituted or unsubstituted siloxane group. Examples of the siloxane group include groups derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane and the like.

When R ¹ is substituted, examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, an alkoxy group, a mercapto group, a cycloalkyl group, a substituted cycloalkyl group, a heterocyclic group, and a substituted heterocyclic group. , Aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, aryloxy group, substituted aryloxy group, halogen atom, haloalkyl group, cyano group, nitro group, nitroso group, amino group, amido group, -C( _{^{O) H, -NR X C (}} O) -N (R X) 2, -OC (O) -N (R X) 2, include an acyl group, oxyacyl group, a carboxyl group, a carbamate group, a sulfonamido group or the like To be Here, R ^X represents a hydrogen atom or an alkyl group. One type or two or more types of these substituents can be selected according to the purpose, application and the like.

R ¹ is, for example, a tetravalent residue of an acid anhydride having two or more anhydride rings in one molecule, that is, from an acid anhydride to an acid anhydride group (—C(═O)OC(= It is preferably a tetravalent group obtained by removing two O)-). Examples of the acid anhydride include the compounds described below.

From the viewpoint of mechanical strength, R ¹ is preferably an aromatic group, and more preferably a residue obtained by removing two acid anhydride groups from pyromellitic dianhydride. That is, the structure (b2) is more preferably a group represented by the following formula (III).

From the viewpoint of fluidity and circuit embeddability, it is preferable that a plurality of structures (b2) are present in the component (A). In that case, the structures (b2) may be the same or different. The number of structures (b2) in the component (A) is preferably 2 to 40, more preferably 2 to 20, and even more preferably 2 to 10.

From the viewpoint of dielectric properties, the structure (b2) may be a group represented by the following formula (IV) or the following formula (V).

The component (A) may be, for example, a compound represented by the following formula (XIII).

In formula (XIII), R represents a saturated or unsaturated divalent hydrocarbon group, and as the saturated or unsaturated divalent hydrocarbon group, the same ones as in the above structure (b1) can be used. R ¹ represents the same tetravalent organic group as ^{R 1} in formula (I), n represents an integer of 1 to 10.

A commercially available compound may be used as the component (A). Examples of commercially available compounds include products manufactured by Digimona Molecule's Incorporated, and specifically, BMI-1500, BMI-1700, BMI-3000, BMI-5000, BMI-9000( All of them are trade names). From the viewpoint of obtaining better high frequency characteristics, it is more preferable to use BMI-3000 as the component (A).

BMI-1500 has a structure represented by formula (XII-1), BMI-1700 has a structure represented by formula (XII-1), and BMI-3000, BMI-5000, and BMI-. 9000 is presumed to have the structure of formula (XII-3). In formula (XII-1) to formula (XII-3), n represents an integer of 1 to 10.

The content of the component (A) in the resin composition is not particularly limited. From the viewpoint of heat resistance, the lower limit of the content of the component (A) may be 2% by mass or more or 10% by mass or more based on the total mass of the resin composition. Further, the upper limit of the content of the component (A) is 98% by mass or less, 50% by mass or less, 30% by mass or less or 20% by mass or less based on the total mass of the resin composition from the viewpoint of the low thermal expansion coefficient. May be. From the viewpoint of heat resistance, the content of the component (A) is preferably 2 to 98% by mass, more preferably 10 to 50% by mass, and 10 to 30% by mass based on the total mass of the resin composition. % Is more preferable, and 10 to 20% by mass is even more preferable.

The molecular weight of the component (A) is not particularly limited. From the viewpoint of fluidity, the lower limit of the weight average molecular weight (Mw) of the component (A) may be 500 or more, 1000 or more, 1500 or more, 1700 or more, 2000 or more, 2500 or more, or 3000 or more. Moreover, the upper limit of Mw of the component (A) may be 10,000 or less, 9000 or less, 7000 or less, or 5000 or less from the viewpoint of handleability. The Mw of the component (A) is preferably 500 to 10,000, more preferably 1,000 to 9000, still more preferably 1,500 to 9,000, from the viewpoints of handleability, fluidity and circuit embedding property. Is more preferably ˜7,000, and particularly preferably 1700 to 5,000.

The Mw of the component (A) can be measured by a gel permeation chromatography (GPC) method.

The measurement conditions of GPC are as follows.
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Guard column and column: TSK Guardcolumn HHR-L+TSKgel G4000HHR+TSKgel G2000HHR [all manufactured by Tosoh Corporation, trade name]
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg/5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL/min Measuring temperature: 40°C

The method for producing the component (A) is not limited. The component (A) may be produced, for example, by reacting an acid anhydride with a diamine to synthesize an amine terminal compound, and then reacting the amine terminal compound with an excess of maleic anhydride.

Examples of the acid anhydride include pyromellitic dianhydride, maleic anhydride, succinic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl. Examples thereof include tetracarboxylic acid dianhydride and 3,3′,4,4′-diphenylsulfone tetracarboxylic acid dianhydride. These acid anhydrides may be used alone or in combination of two or more, depending on the purpose, application, etc. As described above, a tetravalent organic group derived from an acid anhydride as mentioned above can be used as R _{1 in the} above formula (I). From the viewpoint of better dielectric properties, the acid anhydride is preferably pyromellitic dianhydride.

Examples of the diamine include dimer diamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene and 4,4′-bis(4-amino). Phenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 1,4-bis[2-(4 -Aminophenyl)-2-propyl]benzene, polyoxyalkylenediamine, [3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)]cyclohexene and the like. These may be used alone or in combination of two or more, depending on the purpose and application.

<Compound having maleimide group>
The resin composition according to this embodiment may further include a compound having a maleimide group. The compound having a maleimide group according to this embodiment may be referred to as the component (B). In addition, the compound which can correspond to both said (A) component and (B) component shall belong to (A) component. By using the component (B), the resin composition becomes particularly excellent in low thermal expansion. That is, in the resin composition according to the present embodiment, by using the component (A) and the component (B) together, it is possible to further improve low thermal expansion while maintaining good dielectric properties. The reason for this is that the cured product obtained from the resin composition containing the component (A) and the component (B) has a structural unit composed of the component (A) having low dielectric properties and a component (B) having low thermal expansion properties. It is speculated that it includes a polymer having a structural unit consisting of

The component (B) preferably has a lower coefficient of thermal expansion than the component (A). Examples of the component (B) having a lower thermal expansion coefficient than that of the component (A) include a compound having a smaller molecular weight than the component (A), a compound having more aromatic rings than the component (A), and a main chain of (A). The compound etc. which are shorter than the component) are mentioned.

The content of the component (B) in the resin composition is not particularly limited. From the viewpoint of low thermal expansion, the lower limit of the content of the component (B) may be 1% by mass or more, 2% by mass or more, or 3% by mass or more based on the total mass of the resin composition. From the viewpoint of dielectric properties, the upper limit of the content of the component (B) may be 95% by mass or less, 90% by mass or less, or 85% by mass or less based on the total mass of the resin composition. From the viewpoint of low thermal expansion property, the content of the component (B) is preferably 1 to 95% by mass, more preferably 2 to 90% by mass, and more preferably 3 to 85% by mass based on the total mass of the resin composition. More preferably, it is mass %.

The mixing ratio of the component (A) and the component (B) in the resin composition is not particularly limited. From the viewpoint of dielectric properties and low coefficient of thermal expansion, the mass ratio (B)/(A) of the component (A) and the component (B) is preferably 0.01 to 3, and preferably 0.03 to 2. More preferably, it is more preferably 0.05 to 1.

The total content of the component (A) and the component (B) in the resin composition is not particularly limited. From the viewpoint of heat resistance, the lower limit of the total content of the components (A) and (B) may be 2% by mass or more or 10% by mass or more based on the total mass of the resin composition. Moreover, the upper limit of the total content of the components (A) and (B) from the viewpoint of the low thermal expansion coefficient is 98% by mass or less, 50% by mass or less, and 30% by mass or less based on the total mass of the resin composition. Alternatively, it may be 20% by mass or less. From the viewpoint of heat resistance, the total content of the components (A) and (B) is preferably 2 to 98% by mass, and 10 to 50% by mass, based on the total mass of the resin composition. Is more preferable, 10 to 30 mass% is still more preferable, and 10 to 20 mass% is even more preferable.

The component (B) is not particularly limited, and may contain a compound having, in addition to the maleimide group, an aromatic group bonded to the maleimide group, an aliphatic group bonded to the maleimide group, or the like. From the viewpoint of more effectively reducing the coefficient of thermal expansion, the component (B) preferably contains a compound having a maleimide group and an aromatic group bonded to the maleimide group. Since the aromatic group is rigid and has low thermal expansion, the thermal expansion coefficient can be further reduced by using a compound having a maleimide group and an aromatic group bonded to the maleimide group. The compound having a maleimide group is also preferably a polymaleimide compound having two or more maleimide groups.

Specific examples of the compound having a maleimide group as the component (B) include 1,2-dimaleimidoethane, 1,3-dimaleimidopropane, bis(4-maleimidophenyl)methane, and bis(3-ethyl-4-). Maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,7-dimaleimidofluorene, N,N'-(1,3-phenylene)bismaleimide, N,N'- (1,3-(4-methylphenylene))bismaleimide, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ether, 1,3-bis( 3-maleimidophenoxy)benzene, 1,3-bis(3-(3-maleimidophenoxy)phenoxy)benzene, bis(4-maleimidophenyl)ketone, 2,2-bis(4-(4-maleimidophenoxy)phenyl) Propane, bis(4-(4-maleimidophenoxy)phenyl)sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, 4,4′-bis(3-maleimidophenoxy)biphenyl, 1,3-bis( 2-(3-maleimidophenyl)propyl)benzene, 1,3-bis(1-(4-(3-maleimidophenoxy)phenyl)-1-propyl)benzene, bis(maleimidocyclohexyl)methane, 2,2-bis Examples include [4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and bis(maleimidophenyl)thiophene. These may be used alone or in combination of two or more. Among these, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane is preferably used from the viewpoint of further lowering hygroscopicity and thermal expansion coefficient. From the viewpoint of enhancing the breaking strength and the metal foil peeling strength of the resin film formed from the resin composition, it is preferable to use 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane. From the viewpoint of further lowering the hygroscopicity and the coefficient of thermal expansion, it is preferable to use bis(4-maleimidophenyl)methane.

From the viewpoint of moldability, the component (B) preferably contains, for example, a polyamino bismaleimide compound represented by the following formula (VI).

In formula (VI), A ⁴ represents a group represented by the following formula (VII), (VIII), (IX) or (X), and A ⁵ represents a group represented by the following formula (XI).

In formula (VII), R ^10's each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom.

In formula (VIII), R ¹¹ and R ¹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁶ represents an alkylene group having 1 to 5 carbon atoms or an alkylidene group. , An ether group, a sulfide group, a sulfonyl group, a ketone group, a single bond or a group represented by the following formula (VIII-1).

In formula (VIII-1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁷ represents an alkylene group having 1 to 5 carbon atoms, An isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond is shown.

In formula (IX), i represents an integer of 1 to 10.

In formula (X), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j represents an integer of 1 to 8.

In formula (XI), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom, and A ⁸ is , An alkylene group having 1 to 5 carbon atoms, or an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a fluorenylene group, a single bond, a group represented by the following formula (XI-1) or the following formula (XI-2 ) Represents a group represented by.

In formula (XI-1), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom, and A ⁹ represents an alkylene group having 1 to 5 carbon atoms. , Isopropylidene group, m-phenylenediisopropylidene group, p-phenylenediisopropylidene group, ether group, sulfide group, sulfonyl group, ketone group or single bond.

In formula (XI-2), R ^21's each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ¹⁰ and A ¹¹ each independently have 1 to 5 carbon atoms. Represents an alkylene group, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond.

The component (B) is preferably used as the polyamino bismaleimide compound represented by the above formula (VI) from the viewpoints of solubility in organic solvents, high frequency characteristics, high adhesion to conductors, and the like. The polyamino bismaleimide compound is obtained, for example, by subjecting a compound having two maleimide groups at the terminals and an aromatic diamine compound having two primary amino groups in the molecule to a Michael addition reaction in an organic solvent.

The aromatic diamine compound having two primary amino groups in the molecule is not particularly limited, but for example, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline , 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene and the like. These may be used alone or in combination of two or more.

Further, from the viewpoint of high solubility in an organic solvent, high reaction rate during synthesis, and high heat resistance, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl can be used. -Diphenylmethane or 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene are preferred. These may be used alone or in combination of two or more, depending on the purpose and application.

The organic solvent used in producing the polyamino bismaleimide compound is not particularly limited, for example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N,N-dimethylformamide, N, Examples thereof include nitrogen-containing compounds such as N-dimethylacetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Of these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N,N-dimethylformamide and N,N-dimethylacetamide are preferable from the viewpoint of solubility.

<Catalyst>
The resin composition according to the present embodiment may further contain a catalyst for promoting the curing of the component (A). The content of the catalyst is not particularly limited, but may be 0.1 to 5 mass% based on the total mass of the resin composition. As the catalyst, for example, peroxides, azo compounds, zinc compounds (zinc naphthenate, etc.) and the like can be used.

Examples of peroxides include dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di Examples thereof include bis(tert-butylperoxyisopropyl)benzene such as (tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene, and tert-butylhydroperoxide. Examples of the azo compound include 2,2'-azobis(2-methylpropanenitrile), 2,2'-azobis(2-methylbutanenitrile) and 1,1'-azobis(cyclohexanecarbonitrile).

<Thermosetting resin>
The resin composition according to this embodiment may further contain a thermosetting resin different from the component (A) and the component (B). In addition, the compound that can correspond to the component (A) or the component (B) does not belong to the thermosetting resin. By including the thermosetting resin, the low thermal expansion property and the like of the resin composition can be improved.

Examples of the thermosetting resin include epoxy resin and cyanate ester resin. The epoxy resin is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol. Naphthalene skeleton-containing epoxy resin such as novolac type epoxy resin, bisphenol A novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, bifunctional biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin , Dicyclopentadiene type epoxy resin, dihydroanthracene type epoxy resin and the like. These may be used alone or in combination of two or more. Among these, a naphthalene skeleton-containing epoxy resin or a biphenylaralkyl-type epoxy resin is preferable from the viewpoint of high frequency characteristics and thermal expansion characteristics.

The cyanate ester resin is not particularly limited, but for example, 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl) ) Methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α′-bis(4-cyanatophenyl)-m-diisopropylbenzene , A phenol-added dicyclopentadiene polymer cyanate ester compound, a phenol novolac type cyanate ester compound, a cresol novolac type cyanate ester compound, and the like. These thermosetting resins may be used alone or in combination of two or more. Among these, 2,2-bis(4-cyanatophenyl)propane is preferable in consideration of low cost, high frequency characteristics, and total balance of other characteristics.

<Curing agent>
The resin composition according to this embodiment may further contain a curing agent for the thermosetting resin. This makes it possible to smoothly proceed the reaction when obtaining a cured product of the resin composition and to appropriately control the physical properties of the cured product of the obtained resin composition.

When an epoxy resin is used as the thermosetting resin, the curing agent is not particularly limited, but examples thereof include polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, m-phenylenediamine, dicyandiamide; bisphenol A, phenol novolac resin, cresol. Examples thereof include polyphenol compounds such as novolac resin, bisphenol A novolac resin and phenol aralkyl resin; acid anhydrides such as phthalic anhydride and pyromellitic anhydride; various carboxylic acid compounds; various active ester compounds.

When using a cyanate ester resin as the thermosetting resin, the curing agent is not particularly limited, for example, various monophenol compounds, various polyphenol compounds, various amine compounds, various alcohol compounds, various acid anhydrides, various carboxylic acid compounds, etc. Is mentioned. These may be used alone or in combination of two or more.

<Curing accelerator>
The resin composition according to the present embodiment may further contain a curing accelerator depending on the type of the thermosetting resin. Examples of the curing accelerator for the epoxy resin include various imidazoles that are latent thermosetting agents, BF ₃ amine complexes, phosphorus-based curing accelerators, and the like. When a curing accelerator is added, imidazoles and phosphorus-based curing accelerators are preferable from the viewpoint of storage stability of the resin composition, handleability of the semi-cured resin composition, and solder heat resistance.

<Inorganic filler>
The resin composition according to this embodiment may further contain an inorganic filler. By arbitrarily containing an appropriate inorganic filler, low dielectric loss tangent, low thermal expansion, high elastic modulus, heat resistance, flame retardancy, etc. of the resin composition can be more effectively improved. The inorganic filler is not particularly limited, for example, silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, Examples thereof include aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, silicon carbide and borosilicate glass. These may be used alone or in combination of two or more.

The shape and particle size of the inorganic filler are also not particularly limited. The particle size of the inorganic filler may be, for example, 0.01 to 20 μm or 0.1 to 10 μm. Here, the particle size refers to the average particle size, and is the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%. The average particle size can be measured with a particle size distribution measuring device or the like using a laser diffraction scattering method.

When an inorganic filler is used, the amount used is not particularly limited, but for example, the content ratio of the inorganic filler is preferably 3 to 75% by volume, and the solid content in the resin composition is preferably 5 to 70% by volume. % Is more preferable. When the content ratio of the inorganic filler in the resin composition is within the above range, good curability, moldability and chemical resistance are easily obtained.

When an inorganic filler is used, a coupling agent can be used in combination, if necessary, for the purpose of improving the dispersibility of the inorganic filler and the adhesion with the organic component. Such a coupling agent is not particularly limited, and for example, titanate coupling agents, various silane coupling agents, etc. can be used. These may be used alone or in combination of two or more. The amount of the coupling agent used is not particularly limited, and may be, for example, 0.1 to 5 parts by mass or 0.5 to 3 parts by mass with respect to 100 parts by mass of the inorganic filler used. Within this range, the various characteristics are less likely to deteriorate, and the characteristics due to the use of the inorganic filler are likely to be effectively exhibited.

When using a coupling agent, after blending the inorganic filler in the resin composition, the coupling agent is added, may be a so-called integral blend treatment method, the coupling agent to the inorganic filler in advance, A method using a dry or wet surface-treated inorganic filler is preferable. By using this method, the features of the inorganic filler can be more effectively exhibited.

<Thermoplastic resin>
The resin composition according to the present embodiment may further contain a thermoplastic resin from the viewpoint of improving the handleability of the resin film. The type of the thermoplastic resin is not particularly limited, and the molecular weight is not limited, but the number average molecular weight (Mn) is preferably 200 to 60,000 from the viewpoint of further improving the compatibility with the component (A).

From the viewpoint of film forming property and moisture absorption resistance, the thermoplastic resin is preferably a thermoplastic elastomer. Examples of the thermoplastic elastomer include a saturated thermoplastic elastomer, and examples of the saturated thermoplastic elastomer include a chemically modified saturated thermoplastic elastomer and a non-modified saturated thermoplastic elastomer. Examples of the chemically modified saturated thermoplastic elastomer include a styrene-ethylene-butylene copolymer modified with maleic anhydride. Specific examples of the chemically modified saturated thermoplastic elastomer include Tuftec M1911, M1913, M1943 (all manufactured by Asahi Kasei Chemicals Corporation, trade name). On the other hand, examples of the non-modified saturated thermoplastic elastomer include a non-modified styrene-ethylene-butylene copolymer. Specific examples of the unmodified saturated thermoplastic elastomer include Tuftec H1041, H1051, H1043, and H1053 (all manufactured by Asahi Kasei Chemicals Corporation, trade name).

From the viewpoint of film forming property, dielectric property and moisture absorption resistance, the saturated thermoplastic elastomer more preferably has a styrene unit in the molecule. In the present specification, the styrene unit refers to a unit derived from a styrene monomer in the polymer, and the saturated thermoplastic elastomer is an aliphatic hydrocarbon portion other than the aromatic hydrocarbon portion of the styrene unit. Each have a structure constituted by a saturated bonding group.

The content ratio of the styrene unit in the saturated thermoplastic elastomer is not particularly limited, but is a mass percentage of the styrene unit with respect to the total mass of the saturated thermoplastic elastomer, preferably 10 to 80% by mass, and preferably 20 to 70% by mass. It is more preferable to have. When the content ratio of the styrene unit is within the above range, the film appearance, heat resistance and adhesiveness tend to be excellent.

Specific examples of the saturated thermoplastic elastomer having a styrene unit in the molecule include a styrene-ethylene-butylene copolymer. The styrene-ethylene-butylene copolymer can be obtained, for example, by hydrogenating the unsaturated double bond contained in the structural unit derived from butadiene of the styrene-butadiene copolymer.

The content of the thermoplastic resin is not particularly limited, but from the viewpoint of further improving the dielectric properties, the total solid content of the resin composition is preferably 0.1 to 15% by mass, and 0.3 to 10% by mass. % Is more preferable, and 0.5 to 5 mass% is further preferable.

<Flame retardant>
The resin composition according to the present embodiment may further contain a flame retardant. The flame retardant is not particularly limited, but a brominated flame retardant, a phosphorus flame retardant, a metal hydroxide or the like is preferably used. Examples of the brominated flame retardant include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin; hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebistetrabromophthalimide. , 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2,4. Brominated flame retardants such as 6-tris(tribromophenoxy)-1,3,5-triazine; tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromo Examples thereof include bromination reaction type flame retardants containing unsaturated double bond groups such as benzyl acrylate and brominated styrene. These flame retardants may be used alone or in combination of two or more.

As the phosphorus-based flame retardant, aromatic phosphoric acid such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), etc. Ester; Phosphonic acid ester such as divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate; Phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phos Phosphinic acid esters such as faphenanthrene-10-oxide derivatives; phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, Examples thereof include phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus. Examples of the metal hydroxide flame retardant include magnesium hydroxide, aluminum hydroxide and the like. These flame retardants may be used alone or in combination of two or more.

The resin composition according to the present embodiment can be obtained by uniformly dispersing and mixing the above-mentioned components using a solvent as needed, and the preparation means, conditions, etc. are not particularly limited. For example, after agitating and mixing the predetermined components in various amounts sufficiently uniformly with a mixer or the like, kneading is performed using a mixing roll, an extruder, a kneader, a roll, an extruder, etc., and the obtained kneaded product is cooled and cooled. A method of crushing may be mentioned. The kneading method is also not particularly limited. The solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, butanol; ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone. Such as ketones; aromatic hydrocarbons such as toluene, xylene, mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N,N-dimethylformamide, N,N-dimethylacetamide , Organic solvents such as nitrogen-containing compounds such as N-methyl-2-pyrrolidone. These organic solvents may be used alone or in combination of two or more.

The solid content (nonvolatile content) concentration of the resin composition is not particularly limited, but may be, for example, 5 to 80 mass %.

At least one layer of the resin layers according to the present embodiment is a resin layer formed of a semi-cured product or a cured product of the resin composition described above. The laminated body of the present embodiment may have the resin layer only on one side of the glass substrate, or may have the resin layer on both sides of the glass substrate. Further, the laminated body of the present embodiment may include other resin layers in addition to the resin layer.

The resin composition for forming the other resin layer is not particularly limited as long as it does not contain the above-mentioned component (A), and other resins that can be used in the resin composition as required. A component (component (B), catalyst, curing agent, curing accelerator, inorganic filler, flame retardant, etc.) may be contained. The resin may be a thermoplastic resin, a thermosetting resin, or the like, and the thermoplastic resin is modified with a thermosetting resin from the viewpoint of improving dielectric properties, heat resistance, solvent resistance, and press moldability. It may be a resin. As the thermosetting resin and the thermoplastic resin, the same ones as the thermosetting resin and the thermoplastic resin in the resin composition can be used.

Each of the above resin compositions can be obtained by uniformly dispersing and mixing each of the above components using a solvent, if necessary, and the preparation means, conditions and the like are not particularly limited. Although the solvent is not particularly limited, for example, the same solvent as the above-mentioned solvent can be used.

The thickness of the resin layer according to this embodiment is not particularly limited, but for example, 1 to 200 μm is preferable, and 2 to 100 μm is more preferable. By setting the thickness within the above range, not only can the printed wiring board of the present embodiment be made thinner, but also a resin layer having excellent high-speed signal transmission characteristics and high film thickness accuracy can be formed. ..

Examples of the method for manufacturing the laminate of the present embodiment include a method of applying a resin composition to a glass substrate, a method of forming a resin film from the resin composition in advance, and laminating the resin film on the glass substrate. From the viewpoint of ease of production, a method of laminating a resin film on a glass substrate is preferable.

Each manufacturing method will be described in detail below.

The method of applying the resin composition to the glass substrate is a method of applying the resin composition to the surface of the glass substrate to form a resin layer to produce a laminate. For example, a resin varnish is prepared by dissolving and/or dispersing the resin composition in the solvent described above, the resin varnish is applied to a glass substrate using various coaters, and the solvent is dried by heating, blowing hot air, or the like. A resin layer is formed by curing. This resin layer may be in a semi-cured state. In this way, it is possible to manufacture a laminate in which the resin composition is a semi-cured product or a cured product.

The coater used when applying the resin varnish on the glass substrate may be appropriately selected according to the thickness of the resin film to be formed, and examples thereof include a die coater, a comma coater, a bar coater, a kiss coater, and a roll coater. You may

The drying condition after applying the resin varnish on the glass substrate can be, for example, a condition that the content of the solvent in the dried resin film is 10% by mass or less, and is 5% by mass or less. It can be a condition. For example, a resin film can be formed by drying a varnish containing 30 to 60% by mass of a solvent at 50 to 150° C. for about 3 to 10 minutes. Suitable drying conditions can be set in advance by a simple experiment.

The method of laminating the resin film on the glass substrate is a method of producing a laminate by laminating the resin film and the glass substrate using a pressure laminating device such as a vacuum laminator or a roll laminator. The resin film can be manufactured by a known method. For example, there may be mentioned a method in which a resin varnish prepared in the same manner as above is applied to a support using various coaters and dried by heating, blowing hot air or the like. The method of applying the resin varnish to the support and drying it by heating, blowing hot air, or the like may be the same as the method of applying the resin varnish to the glass substrate.

The support of the resin film includes, for example, polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polyethylene naphthalate; films made of polyvinyl chloride, polycarbonate, polyimide, and release paper, copper foil, aluminum foil and the like. Metal foil etc. are mentioned. The support and the protective film described below may be subjected to matte treatment, corona treatment, release treatment and the like.

The thickness of the support may be, for example, 10 to 150 μm, and may be 25 to 50 μm. The thickness of the resin film may be appropriately determined according to the thickness of the resin layer to be formed.

A protective film may be further laminated on the surface of the resin film on which the support is not provided. The protective film may be the same as or different from the material of the support. The thickness of the protective film is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent foreign matter from entering, and it is also possible to wind the resin film into a roll and store it.

When laminating the resin film on the glass substrate, if a protective film is present, the protective film may be peeled off before laminating, and the support may be peeled off after laminating. Further, the resin layer may be cured by further performing heat treatment, if necessary. In this way, a laminate in which the resin composition is a semi-cured product or a cured product can be manufactured.

[Metal-clad laminate]
The metal-clad laminate of the present embodiment includes the above-described laminate of the present embodiment, and a metal foil provided on at least one surface of the resin layer of the laminate opposite to the glass substrate.

(Metal foil)
As the metal foil, for example, copper foil can be used. As the metal foil, those commercially available for printed wiring boards can be used, and the specifications are not particularly limited, but in order to reduce signal transmission loss in the high frequency region, metal foil is used. It is preferable to use a foil having a small surface roughness. By using a metal foil having a small surface roughness, it is possible to reduce the conductor loss due to the roughness of the conductor.

The thickness of the metal foil is not particularly limited, but may be, for example, 1 to 35 μm. When a via hole described below is formed by sandblasting or laser, its thickness is preferably 1 to 5 μm. By reducing the thickness of the metal foil, the through holes can be formed without etching the copper foil.

The size of the metal-clad laminate of the present embodiment is not particularly limited, but from the viewpoint of handleability, a width of 10 to 100 mm and a length of 10 to 3000 mm (when used in a roll, the length is appropriately applied. It is preferable to be selected within the range. In particular, the width is preferably 25 to 550 mm and the length is preferably 25 to 550 mm.

The thickness of the metal-clad laminate of the present embodiment is preferably selected in the range of 35 μm to 1000 mm, more preferably 50 μm to 300 μm, depending on its application.

The metal-clad laminate of the present embodiment is, for example, a resin layer in the laminate of the present embodiment obtained above, a metal foil is laminated on at least one surface opposite to the glass substrate, and a resin component is It can be obtained by curing.

As a method of laminating the metal foil on at least one surface of the resin layer in the laminate, which is opposite to the glass substrate, one or more metal foils are laminated on the above surface, and heated. And/or a method of applying pressure. The metal foil may be formed by laminating metal foils, or may be formed by using a known method such as dry plating.

[Printed wiring board]
The printed wiring board of the present embodiment includes the above-described laminated body of the present embodiment, and a circuit layer provided on at least one surface of the resin layer in the laminated body opposite to the glass substrate.

(Circuit layer)
The circuit layer is not particularly limited, and may be composed of, for example, the above metal foil. As the metal foil, for example, the metal foil applicable to the metal foil-clad laminate described above can be used.

The printed wiring board of the present embodiment can be manufactured using the above laminate according to a method known to those skilled in the art. Hereinafter, the method for manufacturing the printed wiring board of the present embodiment will be described in detail.

(Formation of via holes, etc.)
First, if necessary, the laminated body is perforated by a method such as drilling, sandblasting, laser, electric discharge machining, wet etching, or a combination thereof to form a via hole, a through hole or the like. As the laser, a carbon dioxide gas laser, a YAG laser, a UV laser, an excimer laser, or the like can be used. After forming the via hole and the like, desmear treatment may be performed using an oxidizing agent. Suitable oxidizing agents include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide, sulfuric acid, nitric acid, etc., and potassium permanganate, permanganate A sodium hydroxide aqueous solution such as sodium (alkaline permanganate aqueous solution) is more preferable.

(Formation of wiring pattern)
For forming the wiring pattern, for example, a known subtractive method, a semi-additive method or the like can be used.

When a wiring pattern is formed on the laminate of the present embodiment using the subtractive method, first, the metal-clad laminate of the present embodiment is obtained. After that, an etching resist is formed on the obtained metal-clad laminate, and a metal foil in an unnecessary portion is removed by etching, whereby a circuit layer having a desired wiring pattern is formed and a printed wiring board can be obtained.

When a wiring pattern is formed on the laminated body of the present embodiment by using the semi-additive method, roughening treatment is first performed. As the roughening liquid in this case, use an oxidizing roughening liquid such as a chromium/sulfuric acid roughening liquid, an alkali permanganate roughening liquid, a sodium fluoride/chromium/sulfuric acid roughening liquid, or a borofluoric acid roughening liquid. You can As the roughening treatment, for example, an aqueous solution of diethylene glycol monobutyl ether and NaOH as a swelling liquid is first heated to 70° C. and the laminate is immersed for 5 minutes. Next, as a roughening liquid, an aqueous solution of KMnO ₄ and NaOH is heated to 80° C. and immersed for 10 minutes. Then, it is neutralized by immersing it in a neutralizing solution, for example, a hydrochloric acid aqueous solution of stannous chloride (SnCl ₂ ) at room temperature for 5 minutes.

After the roughening treatment, a plating catalyst application treatment for attaching palladium is performed. The plating catalyst treatment is performed by immersing it in a palladium chloride-based plating catalyst solution. Next, it is immersed in an electroless plating solution to perform an electroless plating treatment for depositing an electroless plating layer having a thickness of 0.3 to 1.5 μm on the surface of the laminate and the entire inside of the via hole or the through hole.

Next, a plating resist is formed and electroplating is performed. Further, the desired wiring pattern can be formed by removing the resist and then removing the electroless plating layer at unnecessary portions by etching. Known electroless plating solutions and plating resists can be used for the electroless plating treatment. Also, a known method can be used for the electroplating treatment. These platings are preferably copper platings.

(Formation of multilayer wiring)
It is also possible to further form a wiring pattern on the laminated body on which the wiring pattern is formed as described above to form a multilayer wiring.

In order to form this multilayer wiring, after laminating the above-mentioned resin film or the like on the laminated body on which the wiring pattern is formed, formation of blind via holes by laser or the like, and interlayer connection by plating or conductive paste, A wiring pattern is formed. In this way, it is possible to manufacture a printed wiring board (multilayer printed wiring board) on which multilayer wiring is formed.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Resin composition (resin varnish)]
Various resin compositions were prepared according to the following procedures. The amounts (parts by mass) of the raw materials used to prepare the resin compositions of Preparation Examples 1 to 7 are summarized in Table 1.

Each component shown in Table 1 was put into a 300 mL four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, stirred at 25° C. for 1 hour, and then filtered through a #200 nylon mesh (opening 75 μm). A resin composition was obtained.

The abbreviations of the materials in Table 1 are as follows.
(1) BMI-1500 [Mw: about 1500, Designer Molecules Inc. Made, product name]
(2) BMI-1700 [Mw: about 1700, Designer Molecules Inc. Made, product name]
(3) BMI-3000 [Mw: about 3000, Designer Molecules Inc. Made, product name]
(4) BMI-5000 [Mw: about 5000, Designer Molecules Inc. Made, product name]
(5) BMI-1000 [bis(4-maleimidophenyl)methane, manufactured by Daiwa Chemical Industry Co., Ltd., trade name]
(6) BMI-4000 [2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, manufactured by Daiwa Kasei Kogyo Co., Ltd.]
(7) NC-3000H [biphenyl aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., trade name]
(8) BADCY [2,2-bis(4-cyanatophenyl)propane, manufactured by Lonza, trade name]
(9) KA1165 [Novolak type phenolic resin, manufactured by DIC Corporation, trade name]
(10) PCP [p-cumylphenol, manufactured by Wako Pure Chemical Industries, Ltd., trade name]
(11) Tuftec H1041 [a hydrogenated product of a styrene-butadiene copolymer having a number average molecular weight of less than 60,000 (styrene content ratio: 30%, Mn: 58000), manufactured by Asahi Kasei Chemicals Corporation, trade name]
(12) Silica slurry [spherical fused silica, surface treatment: phenylaminosilane coupling agent (1% by mass/total solid content in slurry), dispersion medium: methyl isobutyl ketone (MIBK), solid content concentration: 70% by mass, average Particle diameter: 0.5 μm, density: 2.2 g/cm ³ , manufactured by Admatechs Co., Ltd., trade name “SC-2050KNK”]
(13) Perhexin 25B [2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, manufactured by NOF CORPORATION, trade name]
(14) 2E4MZ [2-ethyl-4-methyl-imidazole, manufactured by Shikoku Chemicals Co., Ltd., trade name]
(15) Zinc naphthenate [manufactured by Tokyo Chemical Industry Co., Ltd.]

[Resin film having a resin layer in a semi-cured (B stage) state]
Using a comma coater, the resin varnish obtained above was applied as a support film onto a PET film (G2-38, manufactured by Teijin) having a thickness of 38 μm, and dried at a temperature of 130° C. to obtain a thickness of 50 μm. A resin film with a PET film was produced.

The dielectric property of the resin film was measured by the method shown below.

<Double-sided metal-clad cured resin film>
The PET film of the resin film with the PET film described above is peeled off, two resin films obtained are stacked, and low-profile copper foil with a thickness of 18 μm (F3-WS, M surface Rz: 3 μm, Furukawa Electric Co., Ltd.) Co., Ltd., trade name) is placed so that its roughened (M) surface is in contact, a mirror plate is placed on it, and heat and pressure molding is performed under press conditions of 200° C./3.0 MPa/70 minutes, A metal-clad cured resin film (thickness: 0.1 mm) was produced.

<Characteristic evaluation of double-sided metal-clad cured resin film>
Table 2 shows the results of evaluation of the dielectric properties of the double-sided metal-clad cured resin films obtained from the resin compositions of Preparation Examples 1 to 7 described above. The method of evaluating the dielectric properties is as follows.

<Measurement of dielectric properties (relative permittivity, dielectric loss tangent)>
The dielectric property was measured by etching the outer layer copper foil of the cured resin film by the cavity resonator perturbation method. The conditions were frequency: 10 GHz and 20 GHz, and measurement temperature: 25°C.

As is clear from the results shown in Table 2, the semi-cured resin films obtained from the resin compositions of Preparation Examples 1 to 7 have the relative permittivity and the dielectric constant, which are important characteristics that affect the transmission loss characteristics of high frequency signals. It was confirmed that the tangent was excellent.

(Examples 1 to 7)
[Laminate]
On the PET film of the support, the resin compositions obtained in Preparation Examples 1 to 7 described above were applied and dried in a thickness of 10 μm to prepare a semi-cured resin film with a PET film. Using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho) on both surfaces of a 200 μm thick glass substrate (OA-10G, manufactured by Nippon Electric Glass, width 250 mm x length 250 mm), the resin film with PET film was used. After laminating under the conditions of a vacuum degree of 30 mmHg, a temperature of 130° C. and a pressure of 0.5 MPa, the support film (PET film) is peeled off after cooling to room temperature, and then the resin layer is heated and cured under the conditions of a temperature of 200° C. and a time of 70 minutes. , A laminate was prepared. The laminates produced using the resin films obtained in Preparation Examples 1 to 7 correspond to Examples 1 to 7, respectively.

(Comparative example 1)
As the resin composition, 18.7 g of a biphenylaralkyl type epoxy resin (NC-3000H, manufactured by Nippon Kayaku) and 7.7 g of cresol novolac resin (KA-1165, manufactured by DIC Corporation) were used instead of BMI-3000. Except that 11.3 g of methyl ethyl ketone was used instead of 11.3 g of toluene and 0.53 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemicals Co., Ltd.) was used instead of the organic peroxide. A laminate was prepared in the same manner as in Example 1.

(Comparative example 2)
The copper foil of a glass cloth substrate resin copper-clad laminate (CGN-500, manufactured by Chukoh Chemical Industries, Ltd.) using a notarized thickness of 0.2 mm of a fluororesin was removed by etching to obtain a laminate.

(Comparative example 3)
A copper foil of a glass cloth base resin copper clad laminate (R-5775, manufactured by Panasonic) using a polyphenylene oxide resin having a notable thickness of 0.2 mm was removed by etching to obtain a laminate.

The relative dielectric constant, dielectric loss tangent, thermal expansion coefficient and elastic modulus of the laminates produced in Examples 1 to 7 and Comparative Example 1 and the laminates produced in Comparative Examples 2 and 3 were measured according to the following methods. The results are shown in Table 3.

<Relative permittivity and loss tangent>
The relative permittivity and the dielectric loss tangent were measured by the cavity resonator perturbation method under the conditions of a frequency of 10 GHz and a measurement temperature of 25°C.

<Coefficient of thermal expansion>
The coefficient of thermal expansion was measured as an average coefficient of thermal expansion from 30°C to 150°C by a laser interference method for the laminate and a tensile mode of a thermomechanical analysis method for the laminate.

<Elastic modulus>
The elastic modulus was obtained from a stress-strain curve when measured by a three-point bending test method under the conditions of a span of 3.2 mm, a bending strength of 0.05 mm/min, and a measurement temperature of 25°C.

As is clear from Table 3, the laminate according to the present invention has a low relative dielectric constant and a low dielectric loss tangent, and has low thermal expansion and high elasticity, while it is provided with the resin layer according to the present invention. In Comparative Example 1 which does not have a high relative permittivity and a high dielectric loss tangent.
Further, in Comparative Examples 2 and 3, which are glass cloth base resin laminated plates in which a glass cloth is impregnated with a resin, rather than a laminated body having resin layers on both surfaces of a glass substrate, the coefficient of thermal expansion is large and the elasticity is low became.

From the above, it can be seen that the laminate according to the present invention has low relative permittivity and dielectric loss tangent, and has low thermal expansion and high elasticity. Therefore, a printed wiring board using such a laminated body has excellent high-speed signal transmission characteristics, and has a problem of warpage during mounting as compared with the case of using a conventional glass cloth base resin laminated board. It can be said that it is unlikely to occur.

[Metal-clad laminate]
The PET film of the support was coated with the resin compositions obtained in Preparation Examples 1 to 7 described above to a thickness of 10 μm and dried to prepare a semi-cured resin layer with a PET film.

A semi-cured resin layer with the PET film is arranged on both sides of a glass substrate (OA-10G) so as to be in contact with the glass substrate via the resin layer, and a batch-type vacuum pressure laminator (MVLP-500). Was used for lamination. At this time, the degree of vacuum was 30 mmHg or less, the temperature was 80° C., and the pressure was 0.5 MPa.

After cooling to room temperature, the PET film of the support is peeled off, a carrier copper foil-attached 3 μm copper foil (MT18E×(P)3, manufactured by Mitsui Metal Industry Co., Ltd.) is placed in contact with the resin layer, and vacuum heating is performed. A copper foil was laminated with a press (IMC-1A31, manufactured by Imoto Seisakusho, Ltd.) and the resin layer was cured. At this time, the degree of vacuum was 30 mmHg or less, the temperature was 180° C., the pressurizing time was 120 minutes, and the pressure was 0.1 MPa.

After cooling to room temperature, the carrier copper foil was peeled off to obtain a metal-clad laminate.

10... laminated body, 1... glass substrate, 13a, 13b... resin layer.

Claims (5)

A glass substrate, and a resin layer provided on both sides of the glass substrate,
At least one layer of the resin layer is composed of a resin composition containing a compound having two or more maleimide groups and a divalent group bonded to the maleimide group, and a thermoplastic elastomer . A laminate in which the group contains at least two imide groups other than a saturated or unsaturated divalent hydrocarbon group bonded to the maleimide group and a maleimide group. The laminate according to claim 1, wherein the compound has a weight average molecular weight of 500 to 10,000. The laminate according to claim 1 or 2, wherein the resin composition further contains an inorganic filler. A laminate according to any one of claims 1 to 3, and a metal foil provided on at least one surface of the resin layer in the laminate, which is opposite to the glass substrate, Metal-clad laminate. A laminated body according to any one of claims 1 to 3, and a circuit layer provided on at least one surface of the resin layer in the laminated body opposite to the glass substrate, Printed wiring board.

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